Ion exchangable glass with deep compressive layer and high damage threshold

Abstract

glasses comprising sio₂, Al₂O₃, and P₂O₅ that are capable of chemical strengthened by ion exchange and having high damage resistance. These phosphate-containing glasses have a structure in which silica (sio₂) is replaced by aluminum phosphate (AlPO₄) and/or boron phosphate (BPO₄).

Description

CROSS REFERENCE TO RELATED APPLICATIONS

This application claims the benefit of priority under 35 U.S.C. §119 of U.S. Provisional Application Ser. No. 61/417,941, filed on Nov. 30, 2010, the content of which is relied upon and incorporated herein by reference in its entirety.

BACKGROUND

The disclosure relates to glasses that are damage resistant. More particularly, the disclosure relates to damage resistant phosphate-containing glasses. Even more particularly, the disclosure relates to damage resistant phosphate-containing glasses that are strengthened by ion exchange.

In many applications, glasses are chemically strengthened by ion exchange, which forms a compressive surface layer in the glass. This layer is resistant to the propagation of cracks due impact. Further damage resistance may be provided through the inclusion of boron as B₂O₃ in the composition.

SUMMARY

Glasses comprising SiO₂, Al₂O₃, and P₂O₅ that are capable of chemical strengthening by ion exchange and having high damage resistance are provided. These phosphate-containing glasses have a structure in which silica (SiO₂) in the glass is replaced by aluminum phosphate (AlPO₄), which consists of tetrahedrally coordinated aluminum and phosphorus and/or replaced by boron phosphate (BPO₄), which consists of tetrahedrally coordinated boron and phosphorus. The glasses inherently have Vickers crack initiation (i.e., median and/or radial crack initiation) thresholds of at least 500 gf (gram force). When strengthened by ion exchange, the glasses have Vickers damage resistance thresholds of at least about 10 kgf (kilogram force).

Accordingly, one aspect of the disclosure is to provide a glass. The glass comprises SiO₂, Al₂O₃, P₂O₅, and at least one alkali metal oxide (R₂O), wherein 0.75≦[(P₂O₅(mol %)+R₂O(mol %))/M₂O₃ (mol %)]≦1.3, where M₂O₃=Al₂O₃+B₂O₃.

A second aspect of the disclosure is to provide a glass. The glass comprises SiO₂, Al₂O₃, P₂O₅, and at least one alkali metal oxide (R₂O), wherein 0.75≦[(P₂O₅(mol %)+R₂O(mol %))/M₂O₃ (mol %)]≦1.3, where M₂O₃=Al₂O₃+B₂O₃, and wherein the glass, when ion exchanged, has a Vickers median/radial crack initiation threshold of at least about 10 kgf.

These and other aspects, advantages, and salient features will become apparent from the following detailed description, the accompanying drawings, and the appended claims.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a schematic cross-sectional view of a glass sheet strengthened by ion exchange;

FIG. 2 is a plot of compressive stress and depth of layer as functions of AlPO₄ concentration for 0.7 mm thick phosphate-containing glass samples that were ion exchanged in a molten KNO₃ salt bath at 410° C. for 8 hours;

FIG. 3 is a plot of compressive stress and depth of layer as functions of AlPO₄ concentration for 0.7 mm thick phosphate-containing glass samples that were ion exchanged in a molten KNO₃ salt bath at 450° C. for 1 hour;

FIG. 4 is a plot of compressive stress and depth of layer as functions of AlPO₄ concentration for 0.7 mm thick phosphate-containing glass samples that were ion exchanged in a molten KNO₃ salt bath at 450° C. for 30 minutes; and

FIG. 5 is a plot of Vickers crack initiation threshold as a function of AlPO₄ concentration for boron-free phosphate-containing glasses that were ion exchanged in a molten KNO₃ salt bath at 450° C. for 30 minutes.

DETAILED DESCRIPTION

In the following description, like reference characters designate like or corresponding parts throughout the several views shown in the figures. It is also understood that, unless otherwise specified, terms such as “top,” “bottom,” “outward,” “inward,” and the like are words of convenience and are not to be construed as limiting terms. In addition, whenever a group is described as comprising at least one of a group of elements and combinations thereof, it is understood that the group may comprise, consist essentially of, or consist of any number of those elements recited, either individually or in combination with each other. Similarly, whenever a group is described as consisting of at least one of a group of elements or combinations thereof, it is understood that the group may consist of any number of those elements recited, either individually or in combination with each other. Unless otherwise specified, a range of values, when recited, includes both the upper and lower limits of the range. As used herein, the indefinite articles “a,” “an,” and the corresponding definite article “the” mean “at least one” or “one or more,” unless otherwise specified.

As described herein, the Vickers indenter that is used to measure crack initiation is known in the art and described, for example, in pages 130-132 of “Materials Science and Engineering (third edition)” by William D. Callister (John Wiley & Sons, New York, 1994), which are incorporated by reference herein. Unless otherwise specified, the Vickers indentation cracking threshold measurements described herein are performed by applying and then removing an indentation load to the glass surface at 0.2 mm/min. The indentation maximum load is held for 10 seconds. The indentation cracking threshold is defined at the indentation load at which greater than 50% of 10 indents exhibit any number of radial/median cracks emanating from the corners of the indent impression. The maximum load is increased until the threshold is met for a given glass composition. All indentation measurements are performed at room temperature in 50% relative humidity.

As described herein, abraded ring-on-ring failure loads obtained for glass samples was determined by first blasting the surface of the sample to be studied (typical dimensions are 50 mm×50 mm×0.7 mm thick) with 90 grit silicon carbide (SiC) at a pressure of 5 psi for five seconds. Samples are masked so that the abrasion is limited to a 6 mm diameter circle located at the center of the 50 mm×50 mm faces of the sample. Abrasion of the samples was followed by ring-on-ring load-to failure-testing with a 1 inch diameter support ring and a ½ A inch diameter loading ring. The sample is placed on the support ring with the abraded side face down, so as to put the abraded region in tension during testing. The load is applied at a rate of 1.2 mm/min. Testing is performed at room temperature in 50% relative humidity. The radius of curvature on the rings is 1/16 inch.

Referring to the drawings in general and to FIG. 1 in particular, it will be understood that the illustrations are for the purpose of describing particular embodiments and are not intended to limit the disclosure or appended claims thereto. The drawings are not necessarily to scale, and certain features and certain views of the drawings may be shown exaggerated in scale or in schematic in the interest of clarity and conciseness.

Glasses designed for use in applications such as in consumer electronics, automotive applications, appliances, architectural components, and other areas where high levels of damage resistance are desirable are frequently strengthened by thermal means (e.g., thermal tempering) or chemical means. Ion exchange is widely used to chemically strengthen glass articles for such applications. In this process, a glass article containing a first metal ion (e.g., alkali cations in Li₂O, Na₂O, etc.) is at least partially immersed in or otherwise contacted with an ion exchange bath or medium containing a second metal ion that is either larger or smaller than the first metal ion that is present in the glass. The first metal ions diffuse from the glass surface into the ion exchange bath/medium while the second metal ions from the ion exchange bath/medium replace the first metal ions in the glass to a depth of layer below the surface of the glass. The substitution of larger ions for smaller ions in the glass creates a compressive stress at the glass surface, whereas substitution of smaller ions for larger ions in the glass typically creates a tensile stress at the surface of the glass. In some embodiments, the first metal ion and second metal ion are monovalent alkali metal ions. However, other monovalent metal ions such as Ag⁺, Tl⁺, Cu⁺, and the like may also be used in the ion exchange process.

A cross-sectional view of a portion (i.e., ends of the glass sheet are not shown) of a glass sheet strengthened by ion exchange is schematically shown in FIG. 1. In the non-limiting example shown in FIG. 1, strengthened glass sheet 100 has a thickness t, central portion 115, and a first surface 110 and second surface 120 that are substantially parallel to each other. Compressive layers 112, 122 extend from first surface 110 and second surface 120, respectively, to depths of layer d₁, d₂ below each surface. Compressive layers 112, 122 are under a compressive stress, while central portion 115 is under a tensile stress, or in tension. The tensile stress in central portion 115 balances the compressive stresses in compressive layers 112, 122, thus maintaining equilibrium within strengthened glass sheet 100. Whereas a glass sheet having compressive layers 112, 122 extending from opposite surfaces 110, 120 is shown in FIG. 1, the glass described herein can have a single surface that is strengthened by ion exchange, rather than multiple strengthened surfaces 110, 120. This can be achieved, for example, by masking one of surfaces 110, 120 during ion exchange process.

In order to increase damage resistance, boron is sometimes added to glasses as B₂O₃. However, the presence of B₂O₃ may impede the strengthening of glasses by ion exchange. It has been discovered that addition of phosphorous to the glass as P₂O₅ improves damage resistance and does not impede ion exchange. The addition of phosphorous to the glass creates a structure in which silica (SiO₂ in the glass) is replaced by aluminum phosphate (AlPO₄), which consists of tetrahedrally coordinated aluminum and phosphorus and/or boron phosphate (BPO₄), which consists of tetrahedrally coordinated boron and phosphorus. As described herein, ion exchangeable phosphate-containing glasses, as well as phosphate-containing glasses that are chemically strengthened by ion exchange and having high damage resistance, are provided. These glasses comprise SiO₂, Al₂O₃, P₂O₅, and at least one alkali metal oxide (R₂O, where R is Li, Na, K, Rb, and/or Cs), wherein 0.75≦[(P₂O₅(mol %)+R₂O(mol %))/M₂O₃ (mol %)]≦1.3, where M₂O₃=Al₂O₃+B₂O₃. In some embodiments, [(P₂O₅(mol %)+R₂O (mol %))/M₂O₃ (mol %)]=1. In some embodiments, the glass does not include B₂O₃ and M₂O₃═Al₂O₃. The glass comprises, in some embodiments: about 40 to about 70 mol % SiO₂; 0 to about 28 mol % B₂O₃; about 0 to about 28 mol % Al₂O₃; about 1 to about 14 mol % P₂O₅; and about 12 to about 16 mol % R₂O. In some embodiments, the glass comprises, in some embodiments: about 40 to about 64 mol % SiO₂; 0 to about 8 mol % B₂O₃; about 16 to about 28 mol % Al₂O₃; about 2 to about 12 mol % P₂O₅; and about 12 to about 16 mol % R₂O. The glass may further comprise at least one alkaline earth metal oxide such as, but not limited to, MgO or CaO. Exemplary compositions of the glasses, expressed in mol %, are listed in Table 1. The M₂O₃ content (where M₂O₃=Al₂O₃+B₂O₃), combined P₂O₅+R₂O concentration, (P₂O₅+R₂O)/M₂O₃ ratio, and (P₂O₅+R₂O)/Al₂O₃ ratio of these compositions are also listed in Table 1.

In one aspect, the phosphate-containing glasses described herein have a structure in which silica (SiO₂) in the glass is replaced by aluminum phosphate (AlPO₄), which consists of tetrahedrally coordinated aluminum and phosphorus. Table 1 lists the equivalent concentrations of AlPO₄ units in the glass for compositions given in the table. In such embodiments, the glass compositions described herein follow the rule that Al₂O₃═P₂O₅+R₂O, where Al₂O₃, P₂O₅, and R₂O are compositions expressed in mol %. When such conditions exist within the glass, aluminum will nominally be in the form of either tetrahedral aluminum. The phosphorus and/or alkalis charge compensate aluminum ions so that they have the equivalent of a 4+ charge.

In another aspect, the phosphate-containing glasses described herein have a structure in which silica (SiO₂) is replaced by boron phosphate (BPO₄) in the glass. In such embodiments, the glass compositions described herein follow the rule that Al₂O₃═R₂O and B₂O₃, ═P₂O₅, where Al₂O₃, B₂O₃, P₂O₅, and R₂O are compositions expressed in mol %. When such conditions exist within the glass, boron will nominally be in the form tetrahedral boron phosphate or tetrahedral boron oxide.

In glasses such as those described herein, each alkali metal ion is capable of creating one non-bridging oxygen (NBO). The unit positive charge on an alkali metal ion can be satisfied by an ionic bond to an oxygen in the silicate glass network. This is accomplished by breaking a bridge between adjacent structural units, while donating an oxygen from the R₂O unit. NBOs reduce the connectivity of the glass network. When Al₂O₃ and/or B₂O₃ are added to the glass, the alkali metal ions will charge compensate for the Al³⁺ and/or B³⁺ ions and allow these ions to form tetrahedral structural units. The oxygen supplied by the R₂O units is consumed to form these tetrahedra. Each added aluminum or boron ion will remove one NBO from the glass network. If mol % Al₂O₃+mol % B₂O₃=mol % R₂O, the structure should not contain any NBOs and should be fully linked. Alkalis are preferentially consumed by aluminum over boron. The remaining alkalis convert trigonal boron to tetrahedral boron until [Na₂O(mol %)/B₂O₃(mol %)]>0.5. Accordingly, the glasses described herein are substantially free of NBOs when the above equation is satisfied. Because AlPO₄ and/or BPO₄ are substituted for silica in the glass, the amount of silica in the glasses described herein is lower than in other ion exchangeable glasses.

The phosphate-containing glasses described herein are inherently resistant to damage; i.e., they are damage-resistant in the absence of any thermal or chemical strengthening such as, for example, ion exchange. The phosphate-containing glasses described herein have Vickers indentation damage (crack initiation load) thresholds of at least about 500 gf (gram force) and, in some embodiments, at least about 1000 gf. Vickers indentation cracking thresholds measured for selected prior to strengthening by ion exchange are listed in Table 1.

In some embodiments, the phosphate-containing glasses described herein have molar volumes of at least about 29 cm³/mol, in other embodiments, at least about 30 cm³/mol, and in still other embodiments at least about 32 cm³/mol. Molar volumes of selected glass compositions are listed in Table 1.

The phosphate-containing glasses described herein are also ion exchangeable to a greater depth of compressive layer (depth of layer d₁, d₂ in FIG. 1) below the surface of the glass than soda lime, alkali aluminosilicate, and alkali aluminoborosilicate glasses. The depth of the compressive layer (112, 122 in FIG. 1) has been shown to be a critical factor in crack resistance of cover glasses for portable electronic devices during system level drop tests. In some embodiments, the phosphate-containing glasses are ion exchangeable to a depth of layer of at least 40 μm and, in other embodiments, to a depth of layer of at least about 60 μm. Compressive stresses and depths of layer obtained by ion exchange in a molten KNO₃ salt bath at 410° C. for 8 hours of 0.7 mm thick phosphate-containing glasses (samples 3, 10-13, and 18-20 in Tables 1-3) described herein are plotted as functions of AlPO₄ concentration in FIG. 2. Each of the samples plotted in FIG. 2 contain no boron and have (P₂O₅+R₂₀)/M₂O₃ and (P₂O₅+R₂₀)/Al₂O₃ ratios that are equal to 1. The depth of layer of the compressive surface layer is at least 78 μm and the compressive stress is at least 692 MPa, as determined by photoelastic methods known in the art. Compressive stresses and depths of layer obtained by ion exchange in a molten KNO₃ salt bath at 410° C. for 8 hours of phosphate-containing glasses described herein, as well as Vickers indentation crack initiation loads and abraded ring-on-ring failure load for various P₂O₅ containing glasses are listed in Table 2. In one non-limiting example, a depth of compressive layer of 64 μm is achieved when 0.7 mm thick samples of the phosphate-containing glasses described herein are ion-exchanged in a molten KNO₃ salt bath at 410° C. for 10 hours, whereas a depth of compressive layer of 56 μm is achieved when alkali aluminosilicate glass samples that do not comprise P₂O₅ and having the same thickness undergo ion exchange under the same conditions. When ion exchanged in a molten KNO₃ salt bath at 410° C. for 8 hours, 0.7 mm thick samples of the phosphate-containing glasses described herein have a depth of compressive layer of at least about 60 μm and compressive stress of greater than about 600 MPa. In comparison, 0.7 mm thick samples of alkali aluminosilicate glasses that do not comprise P₂O₅ ion exchange to a compressive depth of layer of 50 μm under the same conditions.

In addition, ion exchange proceeds more quickly in the phosphate-containing glasses described herein than in those glasses where the expression 0.75≦[(P₂O₅(mol %)+R₂O(mol %))/M₂O₃ (mol %)]≦1.3 is not satisfied. In some embodiments, the phosphate-containing glasses described herein, when ion-exchanged for 2 hours at 410° C. in a molten KNO₃ salt bath, are capable of ion exchange to a depth of layer extending to at least about 30 μm from a surface of the glass. Compressive stresses and depths of layer of phosphate-containing glasses described herein, obtained by ion exchange in a molten KNO₃ salt bath at 410° C. for 2 hours, as well as Vickers indentation crack initiation loads are listed in Table 2.

TABLE 1
Compositions of phosphorus-containing glasses
	Sample
mol %	1	2	3	4	5	6	7	8	9	10
SiO2	46	48	50	44	42	49	52	43	40	52
B2O3	4	2	0	6	8	4	4	4	4	0
Al2O3	25	25	25	25	25	23.5	22	26.5	28	24
P2O5	9	9	9	9	9	7.5	6	10.5	12	8
Na2O	14	14	14	14	14	14	14	14	14	14
K2O	2	2	2	2	2	2	2	2	2	2
SnO2	0	0	0	0	0	0	0	0	0	0
AlPO4	18	18	18	18	18	15	12	21	24	16
equivalent
BPO4
equivalent
M2O3	29	27	25	31	33	27.5	26	30.5	32	24
P2O5 + R2O	25	25	25	25	25	23.5	22	26.5	28	24
(P2O5 + R2O)/	0.86	0.93	1.00	0.81	0.76	0.85	0.85	0.87	0.88	1.00
M2O3
(P2O5 + R2O)/	1.00	1.00	1.00	1.00	1.00	1.00	1.00	1.00	1.00	1.00
Al2O3
Molar Volume	33.30	32.97	32.73	33.46	33.58	32.46	31.59	33.98	34.76	32.23
(cm3/mol)
Pre-IX Vickers	500-1000	1000-2000	1000-2000	1000-2000	1000-2000	1000-2000	1000-2000	1000-2000	1000-2000	1000-2000
Crack Initiation
Load (gf)
Anneal Pt. (° C.)	652	698	739	614	572	661	667	650	645	748
Strain Pt. (° C.)	593	637	675	559	521	602	607	593	589	683
Temperature at	1187	1232	1276	1142	1097	1206	1226	1167	1147	1289
Visc = 35
kP (° C.)
Temperature Zircon
Breakdown (° C.)
Liquidus Viscosity
(poise)
	Sample
mol %	11	12	13	14	15	16	17	18	19	20
SiO2	54	56	58	50	50	50	50	60	62	64
B2O3	0	0	0	0	0	0	0	0	0	0
Al2O3	23	22	21	27	23	25	25	20	19	18
P2O5	7	6	5	7	11	9	9	4	3	2
Na2O	14	14	14	14	14	13	15	14	14	14
K2O	2	2	2	2	2	3	1	2	2	2
SnO2	0	0	0	0	0	0	0	0	0	0
AlPO4	14	12	10	14		18	18	8	6	4
equivalent
BPO4
equivalent
M2O3	23	22	21	27	23	25	25	20	19	18
P2O5 + R2O	23	22	21	23	27	25	25	20	19	18
(P2O5 + R2O)/	1.00	1.00	1.00	0.85	1.17	1.00	1.00	1.00	1.00	1.00
M2O3
(P2O5 + R2O)/	1.00	1.00	1.00	0.85	1.17	1.00	1.00	1.00	1.00	1.00
Al2O3
Molar Volume	31.52	31.36	30.7	32.3	33.42	32.91	32.62	30.04	29.38	29.15
(cm3/mol)
Pre-IX Vickers	1000-2000	1000-2000	1000-2000	1000-2000	1000-2000	1000-2000	1000-2000	1000-2000	500-1000	500-1000
Crack Initiation
Load (gf)
Anneal Pt. (° C.)	733.3	740	757	794	685	737	741	770	779	789
Strain Pt. (° C.)	669.3	676	690	725	626	672	678	705	712	722
Temperature at	1303	1316	1317	1312	1241	1278	1275	1338	1359	1377
Visc = 35
kP (° C.)
Temperature Zircon								1135	1130
Breakdown (° C.)
Liquidus Viscosity			1.75E+09					1.18E+14	3.06E+13	6.58E+12
(poise)
	Sample
mol %	21	22	23	24	25	26	27	28	29	30
SiO2	58	60	62	58	60	62	64	58	60	62
B2O3	4	4	4	5	4	3	2	2	2	2
Al2O3	19	18	16	16	16	16	16	20	19	18
P2O5	3	2	2	5	4	3	2	4	3	2
Na2O	14	14	14	14	14	14	14	14	14	14
K2O	2	2	2	2	2	2	2	2	2	2
SnO2	0	0	0	0	0	0	0	0	0	0
AlPO4	6	4						8	6	4
equivalent
BPO4			4	10	8	6	4
equivalent
M2O3	23	22	20	21	20	19	18	22	21	20
P2O5 + R2O	19	18	18	21	20	19	18	20	19	18
(P2O5 + R2O)/	0.83	0.82	0.90	1.00	1.00	1.00	1.00	0.91	0.90	0.90
M2O3
(P2O5 + R2O)/	1.00	1.00	1.13	1.31	1.25	1.19	1.13	1.00	1.00	1.00
Al2O3
Molar Volume	29.61	29.28	29.26	30.39	30.15	29.79	29.08	30.36	30.49	29.35
(cm3/mol)
Pre-IX Vickers	1000-2000	1000-2000	1000-2000	1000-2000	1000-2000	1000-2000	1000-2000	1000-2000	1000-2000	1000-2000
Crack Initiation
Load (gf)
Anneal Pt. (° C.)	669	674	649	602	629	666	699	714	717	723
Strain Pt. (° C.)	606	609	587	545	569	603	633	649	653	656
Temperature at	1259	1277	1273	1223	1251	1293	1329	1289	1309	1323
Visc = 35
kP (° C.)
Temperature Zircon				>1263	1225	1200	1162
Breakdown (° C.)
Liquidus Viscosity	8.04E+08	1.17E+09		9.34E+08	2.89E+09	1.79E+09	6.09E+09	3.98E+11	5.45E+11
(poise)
	Sample
mol %	31	32	33	34	35	36	37	38	39	40
SiO2	59	61	69	69	62	62	59.9	59.88	60	62
B2O3	1	1	3	2	3	3	4	4	4.5	4.5
Al2O3	20	19	12.5	13.5	15	15	16	18	15.5	13.5
P2O5	4	3	3	2	3	3	4	2	4	4
Na2O	14	14	12	13	15	14	15.5	15.5	15.5	15.5
K2O	2	2	0.5	0.5	2	3	0.5	0.5	0.5	0.5
SnO2	0	0	0	0	0	0	0.1	0.1	0	0
AlPO4	8	6						4
equivalent
BPO4			6	4			8	4	8
equivalent
M2O3	21	20	15.5	15.5	18	18	20	22	20	18
P2O5 + R2O	20	19	15.5	15.5	20	20	20	18	20	20
(P2O5 + R2O)/	0.95	0.95	1.00	1.00	1.11	1.11	1.00	0.82	1.00	1.11
M2O3
(P2O5 + R2O)/	1.00	1.00	1.24	1.15	1.33	1.33	1.25	1.00	1.29	1.48
Al2O3
Molar Volume	30.43	29.99	29.06	28.63	29.33	29.52	29.67	29.15	29.72	29.31
(cm3/mol)
Pre-IX Vickers	1000-2000	1000-2000	1000-2000	1000-2000	500-1000	500-1000	1000-2000	1000-2000	1000-2000	1000-2000
Crack Initiation
Load (gf)
Anneal Pt. (° C.)	738	739	656	698	625	639	641	690	616	594
Strain Pt. (° C.)	673	673	589	630	569	581	581	627	561	542
Temperature at	1314	1327	1346	1362	1245	1260	1242	1264	1223	1188
Visc = 35
kP (° C.)
Temperature Zircon				>1255			1225	1110	>1258
Breakdown (° C.)
Liquidus Viscosity	3.48E+12						5.82E+09	3.74E+11	4.91E+09
(poise)
	Sample
mol %	41	42	43	44	45	46	47	48	49	50
SiO2	62	62	62	58	58	58	58	60	60	60
B2O3	2.5	4.5	4.5	4.5	6.5	4.5	4.5	2.5	4.5	4.5
Al2O3	15.5	15.5	15.5	17.5	15.5	15.5	15.5	17.5	17.5	17.5
P2O5	4	2	4	4	4	6	4	4	2	4
Na2O	15.5	15.5	13.5	15.5	15.5	15.5	17.5	15.5	15.5	13.5
K2O	0.5	0.5	0.5	0.5	0.5	0.5	0.5	0.5	0.5	0.5
SnO2	0	0	0	0	0	0	0	0	0	0
AlPO4
equivalent
BPO4
equivalent
M2O3	18	20	20	22	22	20	20	20	22	22
P2O5 + R2O	20	18	18	20	20	22	22	20	18	18
(P2O5 + R2O)/	1.11	0.90	0.90	0.91	0.91	1.10	1.10	1.00	0.82	0.82
M2O3
(P2O5 + R2O)/	1.29	1.16	1.16	1.14	1.29	1.42	1.42	1.14	1.03	1.03
Al2O3
Molar Volume	29.51	28.90	29.92	30.00	29.92	30.5	29.56	29.82	29.21	30.16
(cm3/mol)
Pre-IX Vickers	1000-2000	1000-2000	1000-2000	1000-2000	1000-2000	1000-2000	1000-2000	500-1000	500-1000	1000-2000
Crack Initiation
Load (gf)
Anneal Pt. (° C.)	649	633	638	641	588	592	593	679	666	656
Strain Pt. (° C.)	590	576	577	582	539	542	547	616	606	594
Temperature at	1277	1259	1273	1240	1181.3	1195	1166	1287	1259	1267
Visc = 35
kP (° C.)
Temperature Zircon
Breakdown (° C.)
Liquidus Viscosity							1.50E+08
(poise)
	Sample
mol %	51	52	53	54	55	56	57	58	59	60
SiO2	60	60	60	60	60	60	60	60	60	60
B2O3	6.5	6.5	2.5	2.5	4.5	4.5	4.5	4.5	4.5	4.5
Al2O3	15.5	15.5	15.5	15.5	15.5	15.5	15.4	15.4	15.4	15.4
P2O5	2	4	6	4	6	2	4	4	3.5	4
Na2O	15.5	13.5	15.5	17.5	13.5	17.5	15.5	16	16.5	15.5
K2O	0.5	0.5	0.5	0.5	0.5	0.5	0.5	0	0	0.5
SnO2	0	0	0	0	0	0	0.1	0.1	0.1	0.1
AlPO4
equivalent
BPO4
equivalent
M2O3	22	22	18	18	20	20	19.9	19.9	19.9	19.9
P2O5 + R2O	18	18	22	22	20	20	20	20	20	20
(P2O5 + R2O)/	0.82	0.82	1.22	1.22	1.00	1.00	1.01	1.01	1.01	1.01
M2O3
(P2O5 + R2O)/	1.16	1.16	1.42	1.42	1.29	1.29	1.30	1.30	1.30	1.30
Al2O3
Molar Volume	29.14	30.09	30.28	29.28	30.67	28.79	29.63	29.56	29.30	29.63
(cm3/mol)
Pre-IX Vickers	1000-2000	1000-2000	1000-2000	500-1000	1000-2000	500-1000	1000-2000	1000-2000	1000-2000	1000-2000
Crack Initiation
Load (gf)
Anneal Pt. (° C.)	610	606	630	624	605	623	605	614	613	624
Strain Pt. (° C.)	561	547	572	571	547	571	549	559	559	569
Temperature at	1206	1232	1246	1212	1237	1217	1227	1214	1211	1234
Visc = 35
kP (° C.)
Temperature Zircon										>1250
Breakdown (° C.)
Liquidus Viscosity	3.33E+09						9.74E+08	3.36E+08	1.34E+08	2.20E+10
(poise)
	Sample
	mol %	61	62	63	64	65
	SiO2	58	58.8	58.8	60	60
	B2O3	3.75	4	4	4	4
	Al2O3	16.5	16.3	16.3	15.75	15.75
	P2O5	3.75	4	4	4	4
	Na2O	18	16.4	16.9	15.75	16.25
	K2O	0	0.5	0	0.5	0
	SnO2	0	0	0	0	0
	AlPO4
	equivalent
	BPO4
	equivalent
	M2O3	20.25	20.3	20.3	19.75	19.75
	P2O5 + R2O	21.75	20.9	20.9	20.25	20.25
	(P2O5 + R2O)/	1.07	1.03	1.03	1.03	1.03
	M2O3
	(P2O5 + R2O)/	1.32	1.28	1.28	1.29	1.29
	Al2O3
	Molar Volume	29.63	29.67	29.61	29.64	29.58
	(cm3/mol)
	Pre-IX Vickers	500-1000	1000-2000	1000-2000	1000-2000	1000-2000
	Crack Initiation
	Load (gf)
	Anneal Pt. (° C.)	644	619	619	617	618
	Strain Pt. (° C.)	585	565	565	563	563
	Temperature at	1258	1229	1223	1235	1230
	Visc = 35
	kP (° C.)
	Temperature Zircon
	Breakdown (° C.)
	Liquidus Viscosity	5.29E+09
	(poise)

TABLE II
Table 2. Compressive stress, crack initiation load, and abraded ring-on-ring
failure loads for phosphate containing glasses ion exchanged at 410° C.
Sample	1	2	3	4	5	6	7	8	9	10
410° C. 8 hr ion-exchange on annealed 0.7 mm thick samples
Compressive Stress (MPa)	645	686	698	665	642	697	732	600	638	692
Depth of Layer (microns)	60	62	79	49	45	62	67	52	56	78
Vickers Crack Initiation Load (kgf)	>30	>30	>30	>30	>30	>30	>30	>30	>30	>30
Abraded ring-on-ring load at failure (kgf)	>80	>80	>90	>70	>70	>100	>110	>60	>70	>120
410° C. 2 hr ion-exchange on annealed 0.7 mm thick samples
Compressive Stress (MPa)			711
Depth of Layer (microns)			35
Vickers Crack Initiation Load (kgf)			>30
Sample	11	12	13	14	15	16	17	18	19	20
410° C. 8 hr ion-exchange on annealed 0.7 mm thick samples
Compressive Stress (MPa)	735	740	724	822	618	643	757	794	811	831
Depth of Layer (microns)	84	79	80	75	96	82	67	94	100	103
Vickers Crack Initiation Load (kgf)	>30	>30	>30	>30	>30	>30	>30	>20	>20	15-20
Abraded ring-on-ring load at failure (kgf)	>140	>130	>130	>150	>130	>110	>110	>180	>190	>210
410° C. 2 hr ion-exchange on annealed 0.7 mm thick samples
Compressive Stress (MPa)	774		817					836	838	871
Depth of Layer (microns)	39		42					45	50	53
Vickers Crack Initiation Load (kgf)	>30		>30					25-30	>20	>20
Sample	21	22	23	24	25	26	27	28	29	30
410° C. 8 hr ion-exchange on annealed 0.7 mm thick samples
Compressive Stress (MPa)	833	863	818	675	708	792	848	807	821	862
Depth of Layer (microns)	66	68	72	76	75	84	91	71	78	79
Vickers Crack Initiation Load (kgf)	>30	>30	>30	>30	>25	>25	<20	20-25	20-25	20-25
Abraded ring-on-ring load at failure (kgf)	>130	>140	>140	>110	>110	>160	>190	>130	>150	>170
410° C. 2 hr ion-exchange on annealed 0.7 mm thick samples
Compressive Stress (MPa)	872	897	880
Depth of Layer (microns)	33	34	38
Vickers Crack Initiation Load (kgf)	>30	>30	>30
Sample	31	32	33	34	35	36	37	38	39	40
410° C. 8 hr ion-exchange on annealed 0.7 mm thick samples
Compressive Stress (MPa)	802	838	657	793	763	763	853	981	740	680
Depth of Layer (microns)	81	81	69	71	82	78	68	59	66	64
Vickers Crack Initiation Load (kgf)	20-25	20-25	15-20	20-25	15-20	15-20	>25	>30	>30	>20
Abraded ring-on-ring load at failure (kgf)	>150	>160	>90	>130	>140	>130	>140	>160	>100	>120
410° C. 2 hr ion-exchange on annealed 0.7 mm thick samples
Compressive Stress (MPa)
Depth of Layer (microns)
Vickers Crack Initiation Load (kgf)
Sample	41	42	43	44	45	46	47	48	49	50
410° C. 8 hr ion-exchange on annealed 0.7 mm thick samples
Compressive Stress (MPa)	787	882	740	857	728	672	765	892	951	809
Depth of Layer (microns)	77	59	63	66	56	69	66	74	59	57
Vickers Crack Initiation Load (kgf)	>20	>20	>20	>20	>30	>30	20-25	>20	>20	>20
Abraded ring-on-ring load at failure (kgf)	>140	>130	>100	>140	>80	>90	>110	>170	>150	>100
410° C. 2 hr ion-exchange on annealed 0.7 mm thick samples
Compressive Stress (MPa)					822	735	877
Depth of Layer (microns)					28	35	33
Vickers Crack Initiation Load (kgf)					>30	>30	20-25
Sample	51	52	53	54	55	56	57	58	59	60
410° C. 8 hr ion-exchange on annealed 0.7 mm thick samples
Compressive Stress (MPa)	856	709	690	784	624	852	748	774	793	785
Depth of Layer (microns)	52	54	78	78	64	58	66	63	61	63
Vickers Crack Initiation Load (kgf)	>30	>20	>30	10-15	>20	10-15	>30	>30	>30	>30
Abraded ring-on-ring load at failure (kgf)	>100	>80	>120	>140	>80	>120	>110	>110	>110	>110
410° C. 2 hr ion-exchange on annealed 0.7 mm thick samples
Compressive Stress (MPa)	948
Depth of Layer (microns)	27
Vickers Crack Initiation Load (kgf)	>30
	Sample	61	62	63	64	65
410° C. 8 hr ion-exchange on annealed 0.7 mm thick samples
	Compressive Stress (MPa)	863	796	805	796	787
	Depth of Layer (microns)	64	66	65	65	64
	Vickers Crack Initiation Load (kgf)	>20	>20	>20	>20	>20
	Abraded ring-on-ring load at failure (kgf)	>130	>120	>120	>120	>110
410° C. 2 hr ion-exchange on annealed 0.7 mm thick samples
	Compressive Stress (MPa)
	Depth of Layer (microns)
	Vickers Crack Initiation Load (kgf)

TABLE III
Table 3. Compressive stress, crack initiation load, and abraded ring-on-ring
failure loads for phosphate containing glasses ion exchanged at 450° C.
Sample	1	2	3	4	5	6	7	8	9	10
450° C. 30 min ion-exchange on annealed 0.7 mm thick samples
Compressive Stress (MPa)
Depth of Layer (microns)
Vickers Crack Initiation Load (kgf)
450° C. 1 hr ion-exchange on annealed 0.7 mm thick samples
Compressive Stress (MPa)
Depth of Layer (microns)
Vickers Crack Initiation Load (kgf)
Sample	11	12	13	14	15	16	17	18	19	20
450° C. 30 min ion-exchange on annealed 0.7 mm thick samples
Compressive Stress (MPa)			794					841	843	882
Depth of Layer (microns)			41					39	40	43
Vickers Crack Initiation Load (kgf)			>30					25-30	20-25	15-20
450° C. 1 hr ion-exchange on annealed 0.7 mm thick samples
Compressive Stress (MPa)			803		767			846	848	878
Depth of Layer (microns)			54		36			54	59	61
Vickers Crack Initiation Load (kgf)			>30		>30			>20	20-25	>15
Sample	21	22	23	24	25	26	27	28	29	30
450° C. 30 min ion-exchange on annealed 0.7 mm thick samples
Compressive Stress (MPa)								846	861	916
Depth of Layer (microns)								30	29	32
Vickers Crack Initiation Load (kgf)								20-25	20-25	20-25
450° C. 1 hr ion-exchange on annealed 0.7 mm thick samples
Compressive Stress (MPa)	854	882		704	746	832	875	844	854	897
Depth of Layer (microns)	36	37		40	43	44	47	37	40	42
Vickers Crack Initiation Load (kgf)	>30	>30		>30	>30	>30	<20	20-25	20-25	20-25
Sample	31	32	33	34	35	36	37	38	39	40
450° C. 30 min ion-exchange on annealed 0.7 mm thick samples
Compressive Stress (MPa)	836	856
Depth of Layer (microns)	32	32
Vickers Crack Initiation Load (kgf)	20-25	20-25
450° C. 1 hr ion-exchange on annealed 0.7 mm thick samples
Compressive Stress (MPa)	831	852	680	824	810	760	870	1032
Depth of Layer (microns)	42	43	40	42	46	46	39	32
Vickers Crack Initiation Load (kgf)	20-25	20-25	15-20	20-25	15-20	15-20	>30	>30
Sample	41	42	43	44	45	46	47	48	49	50
450° C. 30 min ion-exchange on annealed 0.7 mm thick samples
Compressive Stress (MPa)
Depth of Layer (microns)
Vickers Crack Initiation Load (kgf)
450° C. 1 hr ion-exchange on annealed 0.7 mm thick samples
Compressive Stress (MPa)					726	678	787
Depth of Layer (microns)					34	42	41
Vickers Crack Initiation Load (kgf)					>30	>30	20-25
Sample	51	52	53	54	55	56	57	58	59	60
450° C. 30 min ion-exchange on annealed 0.7 mm thick samples
Compressive Stress (MPa)
Depth of Layer (microns)
Vickers Crack Initiation Load (kgf)
450° C. 1 hr ion-exchange on annealed 0.7 mm thick samples
Compressive Stress (MPa)	841
Depth of Layer (microns)	31
Vickers Crack Initiation Load (kgf)	>30
Sample	61	62	63	64	65
450° C. 30 min ion-exchange on annealed 0.7 mm thick samples
Compressive Stress (MPa)
Depth of Layer (microns)
Vickers Crack Initiation Load (kgf)
450° C. 1 hr ion-exchange on annealed 0.7 mm thick samples
Compressive Stress (MPa)
Depth of Layer (microns)
Vickers Crack Initiation Load (kgf)

In another aspect, the phosphate-containing glasses described herein have an anneal point (i.e., the temperature at which the viscosity of the glass is 10^12.2 Pascal seconds (Pa·s) (10^13.2 poise (P)) of at least about 600° C., in other aspects, at least about 625° C., and in still other aspects, at least about 645° C., which is greater than those of high strength alkali aluminosilicate glasses and alkali aluminoborosilicate glasses. Anneal points for various compositions are listed in Table 1. The higher anneal point of the presently described glasses also reduces stress relaxation of the glass during ion exchange and enables ion exchange at higher temperatures. The higher anneal points also allows ion exchange of these glasses to be carried out at higher temperatures.

In those embodiments where the glass has a 35 kp temperature (i.e., the temperature at which the glass has a viscosity of 3.5 kPa·s (35 kilopoise (kP)) of less than 1300° C., the glasses described herein may be formed glass by down-draw methods that are known in the art, such as, for example, fusion-drawing and slot-drawing. Alternatively, the phosphate-containing glasses described herein can be formed by other methods known in the art such as, but not limited to, crucible melting, rolling, float methods, or the like. In addition to enabling glass formation by down-draw processes, the higher anneal points allows ion exchange of these glasses to be carried out at higher temperatures.

In some embodiments, the phosphate-containing glasses described herein are down-drawable by processes known in the art, such as slot-drawing, fusion drawing, re-drawing, and the like, and has a liquidus viscosity of at least 130 kilopoise

In some embodiments, the phosphate-containing glasses described herein have a temperature T_35kp at which the glass has a viscosity of 35 kpoise, wherein the temperature T_breakdown at which zircon breaks down to form ZrO₂ and SiO₂ is greater than T^35kp.

FIG. 3 is a plot of compressive stress and depth of layer as functions of AlPO₄ concentration for 0.7 mm thick phosphate-containing glasses (samples 13 and 18-20 in Tables 1-3) phosphate-containing glasses described herein after ion exchange in a molten KNO₃ salt bath for 1 hour at 450° C. As seen in FIG. 3, these glasses are capable of ion exchange under the above conditions to a depth of layer of at least 50 μM and a compressive stress of at least 800 MPa. FIG. 4 is a plot of compressive stress and depth of layer as functions of AlPO₄ concentration for 0.7 mm thick phosphate-containing glasses described herein (samples 13 and 18-20 in Tables 1-3) after ion exchange in a molten KNO₃ salt bath for 30 minutes at 450° C. Compressive stresses and depths of layer obtained by ion exchange in a molten KNO₃ salt bath at 450° C. for 30 minutes and 1 hour of the phosphate-containing glasses described herein, as well as Vickers indentation/crack initiation thresholds and abraded ring-on-ring failure loads for these ion exchange glasses, are listed in Table 3.

In one aspect, the phosphate-containing glasses described herein, when chemically strengthened by ion exchange, exhibit a Vickers initiation cracking threshold of at least about 10 kgf (kilogram force), in some embodiments, at least about 20 kgf, in some embodiments and, in other embodiments, at least about 30 kgf. Vickers initiation cracking thresholds measured for 0.7 mm thick phosphate-containing glasses (samples 13 and 18-20 in Table 1) that were ion exchanged in a molten KNO₃ salt bath at 450° C. for 30 minutes are plotted as a function of AlPO₄ concentration in FIG. 5. Each of the samples for which data are plotted in FIG. 5 do not contain boron and have (P₂O₅+R₂O)/M₂O₃ and (P₂O₅+R₂O)/Al₂O₃ ratios that are equal to 1. In another aspect, the phosphate-containing glasses described herein, when chemically strengthened by ion exchange, fail at loads of greater than about 80 kgf when subjected to an abraded ring-on-ring load.

The glasses described herein may be used in applications such has, but not limited to: touch screens; protective cover glass for electronic devices such as a hand held communication or entertainment devices, information-related terminals, touch sensor devices, or the like; windshields; appliance enclosures; or architectural elements such as windows, panels, or the like.

While typical embodiments have been set forth for the purpose of illustration, the foregoing description should not be deemed to be a limitation on the scope of the disclosure or appended claims. Accordingly, various modifications, adaptations, and alternatives may occur to one skilled in the art without departing from the spirit and scope of the present disclosure or appended claims.

Claims

1. A glass comprising sio₂, 16 to about 28 mol % Al₂O₃, P₂O₅, and at least one alkali metal oxide (R₂O), wherein R₂O is selected from the group consisting of Na₂O and K₂O, wherein 0.75≦[(P₂O₅(mol %)+R₂O(mol %))/M₂O₃ (mol %)]≦1.3, where M₂O₃=Al₂O₃+B₂O₃, and wherein the glass is lithium-free.

2. The glass of claim 1, wherein the glass is ion exchanged, and wherein the glass has a vickers crack initiation threshold of at least about 20 kgf.

3. The glass of claim 1, wherein the glass is ion exchanged to a depth of layer of at least about 40 μm from a surface of the glass.

4. The glass of claim 3, wherein the glass is ion exchanged to a depth of layer extending at least about 60 μm from a surface of the glass.

5. The glass of claim 1, wherein the glass is ion exchanged, and wherein the glass fails at a load of greater than about 80 kgf when subjected to abraded ring-on-ring loading.

6. The glass of claim 1, wherein the glass has an anneal point of at least about 600° C.

7. The glass of claim 1, wherein the glass comprises: about 40 to about 70 mol % sio₂; 0 to about 28 mol % B₂O₃; 16 to about 28 mol % Al₂O₃; about 1 to about 14 mol % P₂O₅; and about 12 to about 18 mol % R₂O.

8. The glass of claim 7, wherein the glass comprises: about 40 to about 64 mol % sio₂; 0 to about 8 mol % B₂O₃; 16 to about 28 mol % Al₂O₃; about 2 to about 12 mol % P₂O₅; and about 12 to about 16 mol % R₂O.

9. The glass of claim 7, wherein the glass further comprises at least one alkaline earth oxide.

10. The glass of claim 1, wherein aluminum is present in the glass in the form of tetrahedral aluminum oxide units and phosphorus is present in the glass in the form of tetrahedral phosphorus oxide units.

11. The glass of claim 10, wherein the tetrahedral aluminum oxide and tetrahedral phosphorus oxide units replace tetrahedral silica units in the glass.

12. The glass of claim 1, wherein boron is present in the glass in the form of tetrahedral boron oxide units and phosphorus is present in the form of tetrahedral phosphorus oxide units.

13. The glass of claim 12, wherein the tetrahedral boron oxide and tetrahedral phosphorus oxide units replace tetrahedral silica units in the glass.

14. The glass of claim 1, wherein the glass is substantially free of non-bridging oxygen atoms.

15. The glass of claim 1, wherein [(P₂O₅(mol %)+R₂O(mol %))/M₂O₃ (mol %)]=1.

16. The glass of claim 1, wherein M₂O₃═Al₂O₃.

17. The glass of claim 1, wherein the molar volume of the glass is at least about 29 cm³/mol.

18. The glass of claim 1, wherein the glass has a depth of layer extending to at least about 30 μm from a surface of the glass when ion exchanged in an ion exchange bath comprising KNO₃ at 410° C. for 2 hours.

19. A glass comprising sio₂, 16 to about 28 mol % Al₂O₃, P₂O₅, and at least one alkali metal oxide (R₂O), wherein R₂O is selected from the group consisting of Na₂O and K₂O, wherein 0.75≦[(P₂O₅(mol %)+R₂O(mol %))/M₂O₃ (mol %)]≦1.3 and M₂O₃=Al₂O₃+B₂O₃, wherein the glass is lithium-free, and wherein the glass, when ion exchanged, has a vickers crack initiation threshold of at least about 10 kgf.

20. The glass of claim 19, wherein the glass is ion exchanged to a depth of layer extending at least about 40 μm from a surface of the glass.

21. The glass of claim 20, wherein the glass is ion exchanged to a depth of layer extending at least about 60 μm from a surface of the glass.

22. The glass of claim 19, wherein the glass is ion exchanged, and wherein the glass fails at a load of greater than about 80 kgf when subjected to abraded ring-on-ring loading.

23. The glass of claim 19, wherein the glass has an anneal point of at least about 600° C.

24. The glass of claim 19, wherein the glass comprises: about 40 to about 70 mol % sio₂; 0 to about 28 mol % B₂O₃; 16 to about 28 mol % Al₂O₃; about 1 to about 14 mol % P₂O₅; and about 12 to about 18 mol % R₂O.

25. The glass of claim 24, wherein the glass comprises: about 40 to about 64 mol % sio₂; 0 to about 8 mol % B₂O₃; 16 to about 28 mol % Al₂O₃; about 2 to about 12 mol % P₂O₅; and about 12 to about 16 mol % R₂O.

26. The glass of claim 24, further comprising at least one alkaline earth oxide.

27. The glass of claim 19, wherein aluminum is present in the glass in the form of tetrahedral aluminum oxide units and phosphorous is present in the glass in the form of tetrahedral phosphorous oxide units.

28. The glass of claim 19, wherein the tetrahedral aluminum oxide and tetrahedral phosphorous oxide units replace tetrahedral silica units in the glass.

29. The glass of claim 19, wherein boron is present in the glass in the form of tetrahedral boron oxide units and phosphorous is present in the glass in the form of tetrahedral phosphorous oxide units.

30. The glass of claim 29, wherein the tetrahedral boron oxide and tetrahedral phosphorous oxide units replace tetrahedral silica units in the glass.

31. The glass of claim 19, wherein the glass is substantially free of non-bridging oxygens.

32. The glass of claim 19, wherein [(P₂O₅(mol %)+R₂O(mol %))/M₂O₃ (mol %)]=1.

33. The glass of claim 19, wherein M₂O₃═Al₂O₃.

34. The glass of claim 19, wherein the glass has a depth of layer extending to at least about 30 μm from a surface of the glass when ion exchanged in an ion exchange bath comprising KNO₃ at 410° C. for 2 hours.